Diodes, and Methods Of Forming Diodes

ABSTRACT

Some embodiments include methods of forming diodes. The methods may include oxidation of an upper surface of a conductive electrode to form an oxide layer over the conductive electrode. In some embodiments, the methods may include formation of an oxidizable material over a conductive electrode, and subsequent oxidation of the oxidizable material to form an oxide layer over the conductive electrode. In some embodiments, the methods may include formation of a metal halide layer over a conductive electrode. Some embodiments include diodes that contain a metal halide layer between a pair of diode electrodes.

TECHNICAL FIELD

Diodes, and methods of forming diodes.

BACKGROUND

Diodes may be utilized in integrated circuitry for numerousapplications. For instance, diodes may be utilized for regulatingcurrent flow, and/or may be utilized as select devices for selectivelyaccessing components of the integrated circuitry.

A class of diodes that is of particular interest are so calledmetal-insulator-metal (MIM) diodes, which are diodes having one or moreelectrically insulative materials sandwiched between a pair ofelectrically conductive electrodes. The electrodes may be defined to bea first electrode and a second electrode. The diodes may be consideredto enable electron flow from the first electrode to the secondelectrode, and to impede electron flow from the second electrode to thefirst electrode. Since current flow is defined to be in the oppositedirection to electron flow; the diodes may also be considered to enablecurrent flow from the second electrode to the first electrode, and toimpede current flow from the first electrode to the second electrode.

A portion of the electrically insulative material between the diodeswill be directly against the first electrode. It is desired that theelectrically insulative material directly against the first electrode byhighly homogenous, and be of high purity, to obtain high reproducibilityof diode characteristics from one diode to another. It is provingdifficult to form the electrically insulative material to the desiredhomogeneity and purity with conventional methods using low temperatureprocesses (i.e., processes at less than 450° C.). For instance, theelectrically insulative material may be conventionally formed by atomiclayer deposition (ALD) of an oxide. The ALD-formed oxide may containcontaminating carbon or other components of precursors utilized in theALD. The contaminating substances may interfere with performance ofdiodes having such oxide incorporated therein.

It is desired to develop new methods for forming electrically insulativematerial of MIM diodes. It is also desired to develop new diodestructures having highly homogenous electrically insulative materialdirectly against the first electrode.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagrammatic, cross-sectional view of a portion of asemiconductor construction illustrating an embodiment.

FIG. 2 is a graphical illustration of current versus voltage for adiode.

FIG. 3 shows three band-gap diagrams illustrating three different biasconditions of a diode in accordance with an embodiment.

FIGS. 4-6 are diagrammatic, cross-sectional views of a portion of adiode at various processing stages of an embodiment.

FIGS. 7-9 are diagrammatic, cross-sectional views of a portion of adiode at various processing stages of an embodiment.

FIGS. 10 and 11 are diagrammatic, cross-sectional views of a portion ofa diode at various processing stages of an embodiment.

DETAILED DESCRIPTION OF THE ILLUSTRATED EMBODIMENTS

In some embodiments, new methods are presented for fabrication of anelectrically insulative material utilized in an MIM diode. An exampleMIM diode 12 is illustrated in FIG. 1. The diode 12 comprises a firstelectrically conductive electrode 17, a second electrically conductiveelectrode 23, and a plurality of electrically insulative layers 3, 5 and7 sandwiched between the first and second electrodes.

The first electrode 17 may comprise one or more electrically conductivematerials having a relatively low work function compared to the secondelectrode; and may, for example, comprise, consist essentially of, orconsist of one or more of aluminum, tantalum, tungsten, tantalumsilicide, and tantalum silicon nitride.

The second electrode 23 may comprise one or more electrically conductivematerials having a relatively high work function compared to the firstelectrode; and may, for example, comprise, consist essentially of, orconsist of one or more of platinum, ruthenium, tantalum nitride,iridium, iridium oxide, ruthenium oxide, molybdenum nitride, andtitanium nitride.

The electrically insulative material closest to the first electrode(specifically, electrically insulative material 3) may comprise anysuitable composition, but is preferably highly homogeneous and pure. Forinstance, insulative material 3 may correspond to a layer of silicondioxide formed to a high level of purity and homogeneity in someembodiments; and in other embodiments may correspond to a layer of metalhalide (for instance, calcium fluoride) formed to a high level of purityand homogeneity.

Electrically insulative material 3 may be desired to be less than orequal to about 20 Å thick, or even less than or equal to about 10 Åthick, in some embodiments.

The electrically insulative materials 5 and 7 may be of any suitablecomposition, and may, for example, comprise, consist essentially of, orconsist of zirconium oxide, hafnium oxide, or titanium oxide. Althoughtwo electrically insulative materials (5 and 7) are shown formed overthe first electrically insulative material 3, in other embodiments theremay be other numbers of electrically insulative materials formed overthe first electrically insulative material. Generally, there will be atleast one electrically insulative material formed over the firstelectrically insulative material 3.

The diode 12 may be part of a semiconductor construction. Specifically,the diode may be formed over a semiconductor substrate (for instance, amonocrystalline silicon wafer) and incorporated into integratedcircuitry supported by the semiconductor substrate. In some embodiments,the diode may be representative of a large array of diodes that aresimultaneously formed over a semiconductor substrate.

A diode, by definition, conducts current between the first and secondelectrodes when voltage of one polarity is applied to the structure, andthat inhibits current flow between the first and second electrodes whenvoltage of an opposite polarity is applied to the structure. FIG. 2shows a graph 2 that diagrammatically illustrates an example embodimentdependence of current flow on voltage for a diode structure of the typeshown in FIG. 1. Specifically, positive voltage may be considered to beone polarity, and negative voltage may be considered to be an oppositepolarity. When positive voltage is applied there is high current flowthrough the structure, and when negative voltage is applied there isrelatively little current flow through the structure. A couple ofexample datapoints “x” and “−x” are shown on the voltage scale. Althoughthe embodiment of FIG. 2 shows increased current flow when positivevoltage is applied and impedance when negative voltage is applied, inother embodiments the increased current flow may occur when negativevoltage is applied and the impedance may occur when positive voltage isapplied.

The various layers of diode 12 may be band-gap engineered to createdesired diode properties. FIG. 3 illustrates how the three layers 3, 5and 7 may be engineered to create desired diode properties.Specifically, FIG. 3 shows band gap diagrams of diode 12 in an unbiasedcondition (diagram 40), a forward biased condition (diagram 42) and areverse biased condition (diagram 44). Diagrams 40 and 44 show that inan unbiased condition, and in a reverse biased condition, bands fromdielectric materials 3, 5 and 7 preclude migration of carriers betweenconductive materials 17 and 23. In contrast, diagram 42 shows thattunneling may occur in a forward biased condition so that carriers(specifically electrons in the shown embodiment) may tunnel fromconductive material 17 to conductive material 23 via quantum wells 43.The flow of the electrons is diagrammatically illustrated with a dashedarrow 45 in FIG. 3.

Various methods may be utilized for forming diodes of the typeillustrated in FIG. 1 as diodes 12. In the prior art, the firstelectrically insulative material 3 often comprises an oxide (forinstance, silicon dioxide); and is formed by atomic layer deposition(ALD) or chemical vapor deposition (CVD). In some embodiments, it isrecognized that ALD or CVD of an oxide introduces contaminants into theoxide, and that cleaner oxides (specifically, oxides having higherpurity and homogeneity) may be formed by oxidizing semiconductormaterials (for instance, silicon), metals (for instance, aluminum) ormetal-containing compositions (for instance, metal silicides and metalnitrides).

An example embodiment is described with reference to FIGS. 4-6.

Referring initially to FIG. 4, such shows a structure 50. The structure50 is electrically conductive, and comprises a surface 51 which is shownto be electrically conductive. The surface may be associated with aregion having a different composition than a remainder of structure 50in some embodiments, and in other embodiments the entirety of structure50 may be of a single homogeneous composition. A dashed line 53 isprovided to diagrammatically illustrate a boundary between a region ofstructure 50 adjacent surface 51 and a remainder of the structure 50.The region adjacent surface 51 is labeled as 54, and the remainder ofstructure 50 is labeled as 52. If structure 50 comprises a homogeneouscomposition throughout (i.e., is a uniform composition throughout), thenregions 52 and 54 will be the same composition as one another.Alternatively, if structure 50 comprises a different compositionadjacent surface 51 than within the remainder of the structure, thenregions 52 and 54 will be of different compositions relative to oneanother.

An example method of forming structure 50 to have a differentcomposition adjacent surface 51 than within the remainder of thestructure is to form the structure by physical vapor deposition (PVD) ofa metal silicide (for instance, tantalum silicide) under conditions thatcreate a gradient of silicon enrichment from one region of the firststructure to another. The shown structure may be silicon rich adjacentsurface 51, and may even consist of silicon along the surface, while theremainder of structure has a substantial amount of metal.

Another example method of forming structure 50 to have a differentcomposition adjacent surface 51 than within the remainder of thestructure is to form the structure to have multiple differentcompositions. Accordingly, the composition formed adjacent surface 51will be different than at least some of the remainder of the structure50. In such embodiments, boundary 53 may separate two differentcompositions one another, rather than delineating regions of a gradient.The composition adjacent surface 51 may comprise an oxidizable material,such as, for example, aluminum or silicon.

The region 54 adjacent surface 51 is oxidized to convert such region tothe first electrically insulative material 3. FIG. 5 shows structure 50after such oxidation.

The oxidation of region 54 (FIG. 4) may comprise any suitablemethodology including, for example, electrochemical methods (forinstance, anodic oxidation), and/or exposure to one or both of O₂ and O₃under oxidative conditions.

In some embodiments, region 54 may comprise, consist essentially of, orconsist of chromium, titanium, aluminum or silicon; and may be convertedto a layer comprising, consist essentially of, or consisting of chromiumoxide, titanium oxide, aluminum oxide or silicon dioxide by anodicoxidation at a temperature of less than or equal to about 450° C.

In other embodiments, region 54 may comprise, consist essentially of, orconsist of silicon rich tantalum silicide, and may be converted to alayer comprising, consisting essentially of, or consisting of eithersilicon or TaSiO_(x); where “x” is greater than zero. The conversion maycomprise anodic oxidation and/or exposure to one or both of O₂ and O₃;and may be conducted at a temperature of less than or equal to about500° C. (for instance, it may comprise an O₂ anneal at a temperature ofabout 480° C. for a few seconds). The low temperature enables avoidanceof phase separation of the tantalum-silicon relative to an amount ofphase separation that may occur at higher temperatures. The lowtemperature may thus form a more homogeneous oxide 3 than would beformed at higher temperatures.

The oxide 3 of FIG. 5 may be formed to a thickness of less than or equalto about 20 Å, and in some embodiments may be formed to a thickness ofless than or equal to about 10 Å. The thickness of oxide 3 may betailored by controlling the aggressiveness of the oxidation conditions,the time of exposure to the oxidation conditions, and/or the thicknessof the region 54 in those embodiments in which region 54 is of adifferent composition to a remainder of structure 50.

An advantage of the processing of the embodiment of FIGS. 4 and 5relative to the prior art is that the embodiment forms oxide byoxidation of metal and/or semiconductor material, rather than by directdeposition of the oxide. Metal and/or semiconductor may be formed to becleaner than oxide in that contaminants (such as carbon) may be betteravoided during deposition of metal and/or semiconductor material thanthey can be during deposition of oxide. Accordingly, the formation ofoxide by oxidation of a metal and/or semiconductor material may lead toa better quality oxide relative to oxides deposited by ALD or CVD.

The region 52 of structure 50 at the processing stage of FIG. 5corresponds to a first electrode 17 of a diode. In some embodiments,other conductive materials may be formed adjacent the region 52 so thatthe region 52 is a part of the first electrode, rather than an entiretyof the first electrode.

FIG. 6 shows a diode 12 formed after subsequent processing to depositone or more electrically insulative layers over oxide 3 (specifically,the insulative layers 5 and 7 are shown in FIG. 6), followed byformation of the second diode electrode 23 over the electricallyinsulative layers. The electrodes 17 and 23, together with oxide 3 andinsulative layers 5 and 7, form a diode; or in other words form aconstruction that conducts current between the first and secondelectrodes when voltage of one polarity is applied to the construction,and that inhibits current flow between the first and second electrodeswhen voltage having a polarity opposite to said one polarity is appliedto the construction.

Another method of forming a diode is described with reference to FIGS.7-9.

FIG. 7 shows a structure 60 comprising a first electrode 17 having anoxidizable material 62 deposited thereover. The oxidizable material may,for example, comprise, consist essentially of, or consist of one or moreof aluminum, chromium, hafnium, magnesium, niobium, silicon, germanium,tantalum, titanium, yttrium and zirconium. In some embodiments, material62 may be referred to as a sacrificial material in that the material 62may be completely oxidized and converted to a new composition. In someembodiments, first electrode 17 may be considered to be a basesupporting material 62.

Material 62 may be deposited by any suitable method, including, forexample, ALD. An advantage to utilizing ALD may be that such can formmaterial 62 to be highly conformal across a surface of first electrode17, and to be very thin. For instance, it may be desired to formmaterial 62 to be of a thickness such that the material 62 may beentirely oxidized to form a layer having a thickness that remains lessthan or equal to about 20 Å.

Referring to FIG. 8, layer 62 (FIG. 7) is oxidized to form the oxidematerial 3. Such oxidation may comprise any suitable methodology, suchas, for example, anodic oxidation and/or exposure to one or both of O₂and O₃. It may be desired to conduct the oxidation at a temperature ofless than or equal to 450° C. to avoid thermally induced problems thatmay occur relative to the compositions of electrode 17 or oxide 3,and/or that may occur relative to other components associated with asemiconductor construction comprising structure 60.

In the shown embodiment, material 3 of FIG. 8 is thicker than thematerial 62 of FIG. 7. Such change in thickness may result from theoxidized material 3 comprising larger molecules relative to thenon-oxidized starting material 62.

FIG. 9 shows a diode 12 formed after subsequent processing to depositone or more electrically insulative layers over oxide 3 (specifically,the insulative layers 5 and 7 are shown in FIG. 9), followed byformation of the second diode electrode 23 over the electricallyinsulative layers. The electrodes 17 and 23, together with oxide 3 andinsulative layers 5 and 7, form a diode; or in other words form aconstruction that conducts current between the first and secondelectrodes when voltage of one polarity is applied to the construction,and that inhibits current flow between the first and second electrodeswhen voltage having a polarity opposite to said one polarity is appliedto the construction.

Another method of forming a diode is described with reference to FIGS.10 and 11.

FIG. 10 shows a structure 70 comprising a first electrically insulativematerial 74 over a first electrode 72.

Electrode 72 may comprise the same compositions as discussed aboveregarding electrode 17 of FIG. 1.

Electrically insulative material 72 comprises one or more metal halides,and may be referred to as a metal halide layer. The metal halides may,for example, comprise, consist essentially of, or consist of one or moreof various metal fluorides; such as one or more compositions selectedfrom the group consisting of calcium fluoride, barium fluoride, lithiumfluoride, magnesium fluoride, lithium beryllium fluoride, sodiumberyllium fluoride, potassium beryllium fluoride, rubidium magnesiumfluoride, strontium lithium fluoride, and barium lithium fluoride.

The metal halides may be formed by any suitable methods. For instance, ametal fluoride (such as calcium fluoride) may be formed by depositingthe metal and then exposing such metal to fluoridation conditions (forinstance, exposure to F₂ at a temperature of less than or equal to about450° C.). Alternatively, the metal halide may be formed by ALD or CVD ofthe metal halide. If ALD or CVD is utilized, it may be desired that suchbe utilized under processing conditions of less than or equal to about450° C. to avoid thermally induced problems that may otherwise occur.

The metal halide may be formed to a thickness of less than or equal toabout 20 Å, and in some embodiments may be formed to a thickness of lessthan or equal to about 10 Å.

Metal halides have appropriate bandgap and dielectric constant to beincorporated as insulative material in MIM diodes, and may be formed tohigh purity and high homogeneity while utilizing relatively lowtemperature (i.e., less than or equal to about 450° C.) conditions.

Referring to FIG. 11, one or more electrically insulative layers areformed over metal halide layer 74 (specifically, two electricallyinsulative layers 76 and 78 are shown), and a second electrode 80 isformed over the electrically insulative layers. The electricallyinsulative layers 76 and 78 may comprise the same compositions asdiscussed above with reference to FIG. 1 for layers 5 and 7; and thesecond electrode 80 may comprise the same compositions as discussed inFIG. 1 for second electrode 23.

The electrodes 72 and 80, together with metal halide layer 74 andinsulative layers 76 and 78, form a diode construction 82 that conductscurrent between the first and second electrodes when voltage of onepolarity is applied to the construction, and that inhibits current flowbetween the first and second electrodes when voltage having a polarityopposite to said one polarity is applied to the construction.

In compliance with the statute, the subject matter disclosed herein hasbeen described in language more or less specific as to structural andmethodical features. It is to be understood, however, that the claimsare not limited to the specific features shown and described, since themeans herein disclosed comprise example embodiments. The claims are thusto be afforded full scope as literally worded, and to be appropriatelyinterpreted in accordance with the doctrine of equivalents.

1-25. (canceled)
 26. A method of forming a diode, comprising: forming ametal silicide-containing structure, the metal silicide-containingstructure having a surface that is silicon rich relative to other metalsilicide of the structure; oxidizing said surface to form SiO₂, andleaving some of the metal silicide not oxidized; the metal silicide thatis not oxidized being at least part of a first electrode; depositing atleast one metal-containing oxide across the SiO₂; forming a secondelectrode over said at least one metal-containing oxide; and wherein thefirst electrode, SiO₂, at least one metal-containing oxide, and secondelectrode together form a construction that conducts current between thefirst and second electrodes when voltage of one polarity is applied tothe construction, and that inhibits current flow between the first andsecond electrodes when voltage having a polarity opposite to said onepolarity is applied to the construction.
 27. The method of claim 26wherein the at least one metal-containing oxide includes one or more ofzirconium oxide, hafnium oxide and titanium oxide.
 28. A method offorming a diode, comprising: forming a tantalum silicide-containingstructure, the tantalum silicide-containing structure having a surfacethat is silicon rich relative to other tantalum silicide of thestructure; oxidizing said surface to form TaSiO_(x), where “x” isgreater than zero, a portion of the tantalum-silicide-containingstructure not being oxidized and being at least a part of a firstelectrode; depositing at least one metal-containing oxide across theTaSiO_(x); forming a second electrode over said at least onemetal-containing oxide; and wherein the first electrode, TaSiO_(x), atleast one metal-containing oxide, and second electrode together form aconstruction that conducts current between the first and secondelectrodes when voltage of one polarity is applied to the construction,and that inhibits current flow between the first and second electrodeswhen voltage having a polarity opposite to said one polarity is appliedto the construction.
 29. The method of claim 28 wherein the at least onemetal-containing oxide includes one or more of zirconium oxide, hafniumoxide and titanium oxide.
 30. A method of forming a diode, comprising:forming a first electrode; forming a metal halide layer over the firstelectrode, the metal halide layer being formed under conditions whichkeep a temperature of the metal halide layer at less than or equal toabout 450° C.; depositing at least one metal-containing oxide across themetal halide layer; forming a second electrode over said at least onemetal-containing oxide; and wherein the first electrode, metal halidelayer, at least one metal-containing oxide, and second electrodetogether form a structure that conducts current between the first andsecond electrodes when voltage of one polarity is applied to thestructure, and that inhibits current flow between the first and secondelectrodes when voltage having a polarity opposite to said one polarityis applied to the structure.
 31. The method of claim 30 wherein themetal halide layer has a thickness of less than or equal to about 20 Å.32. The method of claim 30 wherein the metal halide layer consists ofone or more of calcium fluoride, barium fluoride, lithium fluoride,magnesium fluoride, lithium beryllium fluoride, sodium berylliumfluoride, potassium beryllium fluoride, rubidium magnesium fluoride,strontium lithium fluoride, and barium lithium fluoride.
 33. A diode,comprising: a first electrode; a metal halide layer over and directlyagainst the first electrode; at least one metal-containing oxide overthe metal halide layer; a second electrode over said at least onemetal-containing oxide; and wherein the first electrode, metal halidelayer, at least one metal-containing oxide, and second electrodetogether form a structure that is configured to conduct current betweenthe first and second electrodes when voltage of one polarity is appliedto the structure, and that is configured to inhibit current flow betweenthe first and second electrodes when voltage having a polarity oppositeto said one polarity is applied to the structure.
 34. The diode of claim33 wherein the metal halide layer consists of one or more of calciumfluoride, barium fluoride, lithium fluoride, magnesium fluoride, lithiumberyllium fluoride, sodium beryllium fluoride, potassium berylliumfluoride, rubidium magnesium fluoride, strontium lithium fluoride, andbarium lithium fluoride.